An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3 to syn‐ or anti‐α‐Alkyl‐β‐hydroxy Carbonitriles
Identifieur interne : 001721 ( Istex/Corpus ); précédent : 001720; suivant : 001722An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3 to syn‐ or anti‐α‐Alkyl‐β‐hydroxy Carbonitriles
Auteurs : Renato Dalpozzo ; Giuseppe Bartoli ; Marcella Bosco ; Antonio De Nino ; Antonio Procopio ; Letizia Sambri ; Antonio TagarelliSource :
- European Journal of Organic Chemistry [ 1434-193X ] ; 2001-08.
English descriptors
- KwdEn :
- Amino alcohols, Carbonitriles, Carbonyl function, Cdcl3, Chem, Chloride molar ratio, Complete reduction, Conformation, Crude mixture, Cyano, Cyano group, Dalpozzo, Diastereoisomeric mixtures, Diastereoisomeric ratio, Dihedral angle, Dramatic decrease, Electronic repulsions, Eluent light ether, Flash column chromatography, Full paper, Functionalized ketones, Hydroxy carbonitriles, Isomer, Keto, Keto carbonitrile, Keto carbonitriles, Keto phosphane, Large variety, Lewis acid, Libh4, Minor isomer, More peaks, Nitrile function, Orthogonal position, Other hand, Phenyl frameworks, Pure diastereoisomers, Pure diastereomeric mixture, Reaction times, Room temperature, Stereochemical outcome, Steric interactions.
- Teeft :
- Amino alcohols, Carbonitriles, Carbonyl function, Cdcl3, Chem, Chloride molar ratio, Complete reduction, Conformation, Crude mixture, Cyano, Cyano group, Dalpozzo, Diastereoisomeric mixtures, Diastereoisomeric ratio, Dihedral angle, Dramatic decrease, Electronic repulsions, Eluent light ether, Flash column chromatography, Full paper, Functionalized ketones, Hydroxy carbonitriles, Isomer, Keto, Keto carbonitrile, Keto carbonitriles, Keto phosphane, Large variety, Lewis acid, Libh4, Minor isomer, More peaks, Nitrile function, Orthogonal position, Other hand, Phenyl frameworks, Pure diastereoisomers, Pure diastereomeric mixture, Reaction times, Room temperature, Stereochemical outcome, Steric interactions.
Abstract
α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to syn‐ and anti‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl4 in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the syn‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl3 in coordinating solvents such as THF, followed by reduction with LiBH4, predominantly led to the anti‐isomers, in agreement with an open‐chain transition state. The reduction to syn‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.
Url:
DOI: 10.1002/1099-0690(200108)2001:15<2971::AID-EJOC2971>3.0.CO;2-K
Links to Exploration step
ISTEX:26CE9E5B00386D4F6B6B388D61F0037923F49C27Le document en format XML
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Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy</mods:affiliation></affiliation></author><author><name sortKey="De Nino, Antonio" sort="De Nino, Antonio" uniqKey="De Nino A" first="Antonio" last="De Nino">Antonio De Nino</name><affiliation><mods:affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</mods:affiliation></affiliation></author><author><name sortKey="Procopio, Antonio" sort="Procopio, Antonio" uniqKey="Procopio A" first="Antonio" last="Procopio">Antonio Procopio</name><affiliation><mods:affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</mods:affiliation></affiliation></author><author><name sortKey="Sambri, Letizia" sort="Sambri, Letizia" uniqKey="Sambri L" first="Letizia" last="Sambri">Letizia Sambri</name><affiliation><mods:affiliation>Dipartimento di Chimica Organica ′A. Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy</mods:affiliation></affiliation></author><author><name sortKey="Tagarelli, Antonio" sort="Tagarelli, Antonio" uniqKey="Tagarelli A" first="Antonio" last="Tagarelli">Antonio Tagarelli</name><affiliation><mods:affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">European Journal of Organic Chemistry</title><title level="j" type="alt">EUROPEAN JOURNAL OF ORGANIC CHEMISTRY</title><idno type="ISSN">1434-193X</idno><idno type="eISSN">1099-0690</idno><imprint><biblScope unit="vol">2001</biblScope><biblScope unit="issue">15</biblScope><biblScope unit="page" from="2971">2971</biblScope><biblScope unit="page" to="2976">2976</biblScope><biblScope unit="page-count">6</biblScope><publisher>WILEY‐VCH Verlag GmbH</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2001-08">2001-08</date></imprint><idno type="ISSN">1434-193X</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1434-193X</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Amino alcohols</term><term>Carbonitriles</term><term>Carbonyl function</term><term>Cdcl3</term><term>Chem</term><term>Chloride molar ratio</term><term>Complete reduction</term><term>Conformation</term><term>Crude mixture</term><term>Cyano</term><term>Cyano group</term><term>Dalpozzo</term><term>Diastereoisomeric mixtures</term><term>Diastereoisomeric ratio</term><term>Dihedral angle</term><term>Dramatic decrease</term><term>Electronic repulsions</term><term>Eluent light ether</term><term>Flash column chromatography</term><term>Full paper</term><term>Functionalized ketones</term><term>Hydroxy carbonitriles</term><term>Isomer</term><term>Keto</term><term>Keto carbonitrile</term><term>Keto carbonitriles</term><term>Keto phosphane</term><term>Large variety</term><term>Lewis acid</term><term>Libh4</term><term>Minor isomer</term><term>More peaks</term><term>Nitrile function</term><term>Orthogonal position</term><term>Other hand</term><term>Phenyl frameworks</term><term>Pure diastereoisomers</term><term>Pure diastereomeric mixture</term><term>Reaction times</term><term>Room temperature</term><term>Stereochemical outcome</term><term>Steric interactions</term></keywords><keywords scheme="Teeft" xml:lang="en"><term>Amino alcohols</term><term>Carbonitriles</term><term>Carbonyl function</term><term>Cdcl3</term><term>Chem</term><term>Chloride molar ratio</term><term>Complete reduction</term><term>Conformation</term><term>Crude mixture</term><term>Cyano</term><term>Cyano group</term><term>Dalpozzo</term><term>Diastereoisomeric mixtures</term><term>Diastereoisomeric ratio</term><term>Dihedral angle</term><term>Dramatic decrease</term><term>Electronic repulsions</term><term>Eluent light ether</term><term>Flash column chromatography</term><term>Full paper</term><term>Functionalized ketones</term><term>Hydroxy carbonitriles</term><term>Isomer</term><term>Keto</term><term>Keto carbonitrile</term><term>Keto carbonitriles</term><term>Keto phosphane</term><term>Large variety</term><term>Lewis acid</term><term>Libh4</term><term>Minor isomer</term><term>More peaks</term><term>Nitrile function</term><term>Orthogonal position</term><term>Other hand</term><term>Phenyl frameworks</term><term>Pure diastereoisomers</term><term>Pure diastereomeric mixture</term><term>Reaction times</term><term>Room temperature</term><term>Stereochemical outcome</term><term>Steric interactions</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to syn‐ and anti‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl4 in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the syn‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl3 in coordinating solvents such as THF, followed by reduction with LiBH4, predominantly led to the anti‐isomers, in agreement with an open‐chain transition state. The reduction to syn‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.</div></front></TEI><istex><corpusName>wiley</corpusName><keywords><teeft><json:string>carbonitriles</json:string><json:string>chem</json:string><json:string>cdcl3</json:string><json:string>keto</json:string><json:string>isomer</json:string><json:string>libh4</json:string><json:string>cyano</json:string><json:string>dalpozzo</json:string><json:string>cyano group</json:string><json:string>full paper</json:string><json:string>room temperature</json:string><json:string>stereochemical outcome</json:string><json:string>complete reduction</json:string><json:string>conformation</json:string><json:string>functionalized ketones</json:string><json:string>keto carbonitriles</json:string><json:string>amino alcohols</json:string><json:string>keto phosphane</json:string><json:string>lewis acid</json:string><json:string>eluent light ether</json:string><json:string>carbonyl function</json:string><json:string>other hand</json:string><json:string>nitrile function</json:string><json:string>large variety</json:string><json:string>keto carbonitrile</json:string><json:string>diastereoisomeric ratio</json:string><json:string>crude mixture</json:string><json:string>chloride molar ratio</json:string><json:string>dramatic decrease</json:string><json:string>steric interactions</json:string><json:string>dihedral angle</json:string><json:string>orthogonal position</json:string><json:string>phenyl frameworks</json:string><json:string>electronic repulsions</json:string><json:string>minor isomer</json:string><json:string>flash column chromatography</json:string><json:string>hydroxy carbonitriles</json:string><json:string>diastereoisomeric mixtures</json:string><json:string>pure diastereoisomers</json:string><json:string>pure diastereomeric mixture</json:string><json:string>more peaks</json:string><json:string>reaction times</json:string></teeft></keywords><author><json:item><name>Renato Dalpozzo</name><affiliations><json:string>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</json:string><json:string>E-mail: dalpozzo@unical.it</json:string></affiliations></json:item><json:item><name>Giuseppe Bartoli</name><affiliations><json:string>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</json:string></affiliations></json:item><json:item><name>Marcella Bosco</name><affiliations><json:string>Dipartimento di Chimica Organica ′A. Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy</json:string></affiliations></json:item><json:item><name>Antonio De Nino</name><affiliations><json:string>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</json:string></affiliations></json:item><json:item><name>Antonio Procopio</name><affiliations><json:string>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</json:string></affiliations></json:item><json:item><name>Letizia Sambri</name><affiliations><json:string>Dipartimento di Chimica Organica ′A. Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy</json:string></affiliations></json:item><json:item><name>Antonio Tagarelli</name><affiliations><json:string>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Cyanides</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Reductions</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Asymmetric synthesis</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Lewis acids</value></json:item></subject><articleId><json:string>EJOC2971</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>article</json:string></originalGenre><abstract>α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to syn‐ and anti‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl4 in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the syn‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl3 in coordinating solvents such as THF, followed by reduction with LiBH4, predominantly led to the anti‐isomers, in agreement with an open‐chain transition state. The reduction to syn‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.</abstract><qualityIndicators><score>4.841</score><pdfVersion>1.2</pdfVersion><pdfPageSize>595 x 794 pts</pdfPageSize><refBibsNative>true</refBibsNative><abstractCharCount>700</abstractCharCount><pdfWordCount>3773</pdfWordCount><pdfCharCount>23405</pdfCharCount><pdfPageCount>6</pdfPageCount><abstractWordCount>89</abstractWordCount></qualityIndicators><title>An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3 to syn‐ or anti‐α‐Alkyl‐β‐hydroxy Carbonitriles</title><genre><json:string>article</json:string></genre><host><title>European Journal of Organic Chemistry</title><language><json:string>unknown</json:string></language><doi><json:string>10.1002/(ISSN)1099-0690</json:string></doi><issn><json:string>1434-193X</json:string></issn><eissn><json:string>1099-0690</json:string></eissn><publisherId><json:string>EJOC</json:string></publisherId><volume>2001</volume><issue>15</issue><pages><first>2971</first><last>2976</last><total>6</total></pages><genre><json:string>journal</json:string></genre><subject><json:item><value>Full Paper</value></json:item></subject></host><categories><wos><json:string>science</json:string><json:string>chemistry, organic</json:string></wos><scienceMetrix><json:string>natural sciences</json:string><json:string>chemistry</json:string><json:string>organic chemistry</json:string></scienceMetrix><inist><json:string>sciences appliquees, technologies et medecines</json:string><json:string>sciences biologiques et medicales</json:string><json:string>sciences biologiques fondamentales et appliquees. psychologie</json:string><json:string>vecteurs d'importance medicale, nuisances, depredateurs des denrees et materiaux: surveillance des populations et lutte</json:string></inist></categories><publicationDate>2001</publicationDate><copyrightDate>2001</copyrightDate><doi><json:string>10.1002/1099-0690(200108)2001:15>2971::AID-EJOC2971>3.0.CO;2-K</json:string></doi><id>26CE9E5B00386D4F6B6B388D61F0037923F49C27</id><score>1</score><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api.istex.fr/document/26CE9E5B00386D4F6B6B388D61F0037923F49C27/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api.istex.fr/document/26CE9E5B00386D4F6B6B388D61F0037923F49C27/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/26CE9E5B00386D4F6B6B388D61F0037923F49C27/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl<hi rend="subscript">4</hi>/BH<hi rend="subscript">3</hi> or LiBH<hi rend="subscript">4</hi>/CeCl<hi rend="subscript">3</hi> to <hi rend="italic">syn</hi>‐ or <hi rend="italic">anti</hi>‐α‐Alkyl‐β‐hydroxy Carbonitriles</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag GmbH</publisher><pubPlace>Weinheim</pubPlace><availability><licence>© 2001 WILEY‐VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany</licence></availability><date type="published" when="2001-08"></date></publicationStmt><notesStmt><note type="content-type" subtype="article" source="article" scheme="https://content-type.data.istex.fr/ark:/67375/XTP-6N5SZHKN-D">article</note><note type="publication-type" subtype="journal" scheme="https://publication-type.data.istex.fr/ark:/67375/JMC-0GLKJH51-B">journal</note></notesStmt><sourceDesc><biblStruct type="article"><analytic><title level="a" type="main" xml:lang="en">An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl<hi rend="subscript">4</hi>/BH<hi rend="subscript">3</hi> or LiBH<hi rend="subscript">4</hi>/CeCl<hi rend="subscript">3</hi> to <hi rend="italic">syn</hi>‐ or <hi rend="italic">anti</hi>‐α‐Alkyl‐β‐hydroxy Carbonitriles</title><title level="a" type="short" xml:lang="en">Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3</title><author xml:id="author-0000"><persName><forename type="first">Renato</forename><surname>Dalpozzo</surname></persName><email>dalpozzo@unical.it</email><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044<address><country key="IT"></country></address></affiliation></author><author xml:id="author-0001"><persName><forename type="first">Giuseppe</forename><surname>Bartoli</surname></persName><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044<address><country key="IT"></country></address></affiliation></author><author xml:id="author-0002"><persName><forename type="first">Marcella</forename><surname>Bosco</surname></persName><affiliation>Dipartimento di Chimica Organica ′A. Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy<address><country key="IT"></country></address></affiliation></author><author xml:id="author-0003"><persName><forename type="first">Antonio</forename><surname>De Nino</surname></persName><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044<address><country key="IT"></country></address></affiliation></author><author xml:id="author-0004"><persName><forename type="first">Antonio</forename><surname>Procopio</surname></persName><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044<address><country key="IT"></country></address></affiliation></author><author xml:id="author-0005"><persName><forename type="first">Letizia</forename><surname>Sambri</surname></persName><affiliation>Dipartimento di Chimica Organica ′A. Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy<address><country key="IT"></country></address></affiliation></author><author xml:id="author-0006"><persName><forename type="first">Antonio</forename><surname>Tagarelli</surname></persName><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044<address><country key="IT"></country></address></affiliation></author><idno type="istex">26CE9E5B00386D4F6B6B388D61F0037923F49C27</idno><idno type="ark">ark:/67375/WNG-7RVDSGG5-7</idno><idno type="DOI">10.1002/1099-0690(200108)2001:15<2971::AID-EJOC2971>3.0.CO;2-K</idno><idno type="unit">EJOC2971</idno><idno type="toTypesetVersion">file:EJOC.EJOC2971.pdf</idno></analytic><monogr><title level="j" type="main">European Journal of Organic Chemistry</title><title level="j" type="alt">EUROPEAN JOURNAL OF ORGANIC CHEMISTRY</title><idno type="pISSN">1434-193X</idno><idno type="eISSN">1099-0690</idno><idno type="book-DOI">10.1002/(ISSN)1099-0690</idno><idno type="book-part-DOI">10.1002/1099-0690(200108)2001:15<>1.0.CO;2-9</idno><idno type="product">EJOC</idno><imprint><biblScope unit="vol">2001</biblScope><biblScope unit="issue">15</biblScope><biblScope unit="page" from="2971">2971</biblScope><biblScope unit="page" to="2976">2976</biblScope><biblScope unit="page-count">6</biblScope><publisher>WILEY‐VCH Verlag GmbH</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2001-08"></date></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><abstract xml:lang="en" style="main"><head>Abstract</head><p>α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to <hi rend="italic">syn</hi>‐ and <hi rend="italic">anti</hi>‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl<hi rend="subscript">4</hi> in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the<hi rend="italic"> syn</hi>‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl<hi rend="subscript">3</hi> in coordinating solvents such as THF, followed by reduction with LiBH<hi rend="subscript">4</hi>, predominantly led to the <hi rend="italic">anti</hi>‐isomers, in agreement with an open‐chain transition state. The reduction to <hi rend="italic">syn</hi>‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.</p></abstract><textClass><keywords xml:lang="en"><term xml:id="kwd1">Cyanides</term><term xml:id="kwd2">Reductions</term><term xml:id="kwd3">Asymmetric synthesis</term><term xml:id="kwd4">Lewis acids</term></keywords><keywords rend="articleCategory"><term>Full Paper</term></keywords></textClass><langUsage><language ident="en"></language></langUsage></profileDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api.istex.fr/document/26CE9E5B00386D4F6B6B388D61F0037923F49C27/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Wiley, elements deleted: body"><istex:xmlDeclaration>version="1.0" encoding="UTF-8" standalone="yes"</istex:xmlDeclaration><istex:document><component version="2.0" type="serialArticle" xml:lang="en"><header><publicationMeta level="product"><publisherInfo><publisherName>WILEY‐VCH Verlag GmbH</publisherName><publisherLoc>Weinheim</publisherLoc></publisherInfo><doi registered="yes">10.1002/(ISSN)1099-0690</doi><issn type="print">1434-193X</issn><issn type="electronic">1099-0690</issn><idGroup><id type="product" value="EJOC"></id></idGroup><titleGroup><title type="main" xml:lang="en" sort="EUROPEAN JOURNAL OF ORGANIC CHEMISTRY">European Journal of Organic Chemistry</title><title type="short">Eur. J. Org. Chem.</title></titleGroup></publicationMeta><publicationMeta level="part" position="150"><doi origin="wiley" registered="yes">10.1002/1099-0690(200108)2001:15<>1.0.CO;2-9</doi><numberingGroup><numbering type="journalVolume" number="2001">2001</numbering><numbering type="journalIssue">15</numbering></numberingGroup><coverDate startDate="2001-08">August 2001</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="22" status="forIssue"><doi origin="wiley" registered="yes">10.1002/1099-0690(200108)2001:15<2971::AID-EJOC2971>3.0.CO;2-K</doi><idGroup><id type="unit" value="EJOC2971"></id></idGroup><countGroup><count type="pageTotal" number="6"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title></titleGroup><copyright ownership="publisher">© 2001 WILEY‐VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany</copyright><eventGroup><event type="manuscriptReceived" date="2001-02-08"></event><event type="firstOnline" date="2001-07-10"></event><event type="publishedOnlineFinalForm" date="2001-07-10"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.3.6 mode:FullText source:FullText result:FullText" date="2010-04-19"></event><event type="xmlConverted" agent="Converter:WILEY_ML3G_TO_WILEY_ML3GV2 version:3.8.8" date="2014-01-24"></event><event type="xmlConverted" agent="Converter:WML3G_To_WML3G version:4.1.7 mode:FullText,remove_FC" date="2014-10-16"></event></eventGroup><numberingGroup><numbering type="pageFirst">2971</numbering><numbering type="pageLast">2976</numbering></numberingGroup><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:EJOC.EJOC2971.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="2"></count><count type="tableTotal" number="3"></count><count type="referenceTotal" number="26"></count></countGroup><titleGroup><title type="main" xml:lang="en">An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl<sub>4</sub>/BH<sub>3</sub> or LiBH<sub>4</sub>/CeCl<sub>3</sub> to <i>syn</i>‐ or <i>anti</i>‐α‐Alkyl‐β‐hydroxy Carbonitriles</title><title type="short" xml:lang="en">Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl<sub>4</sub>/BH<sub>3</sub> or LiBH<sub>4</sub>/CeCl<sub>3</sub></title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Renato</givenNames><familyName>Dalpozzo</familyName></personName><contactDetails><email>dalpozzo@unical.it</email></contactDetails></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Giuseppe</givenNames><familyName>Bartoli</familyName></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Marcella</givenNames><familyName>Bosco</familyName></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Antonio</givenNames><familyName>De Nino</familyName></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Antonio</givenNames><familyName>Procopio</familyName></personName></creator><creator xml:id="au6" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Letizia</givenNames><familyName>Sambri</familyName></personName></creator><creator xml:id="au7" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Antonio</givenNames><familyName>Tagarelli</familyName></personName></creator></creators><affiliationGroup><affiliation xml:id="af1" countryCode="IT" type="organization"><unparsedAffiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</unparsedAffiliation></affiliation><affiliation xml:id="af2" countryCode="IT" type="organization"><unparsedAffiliation>Dipartimento di Chimica Organica ′A. Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">Cyanides</keyword><keyword xml:id="kwd2">Reductions</keyword><keyword xml:id="kwd3">Asymmetric synthesis</keyword><keyword xml:id="kwd4">Lewis acids</keyword></keywordGroup><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to <i>syn</i>‐ and <i>anti</i>‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl<sub>4</sub> in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the<i> syn</i>‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl<sub>3</sub> in coordinating solvents such as THF, followed by reduction with LiBH<sub>4</sub>, predominantly led to the <i>anti</i>‐isomers, in agreement with an open‐chain transition state. The reduction to <i>syn</i>‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.</p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3 to syn‐ or anti‐α‐Alkyl‐β‐hydroxy Carbonitriles</title></titleInfo><titleInfo type="abbreviated" lang="en"><title>Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3 to syn‐ or anti‐α‐Alkyl‐β‐hydroxy Carbonitriles</title></titleInfo><name type="personal"><namePart type="given">Renato</namePart><namePart type="family">Dalpozzo</namePart><affiliation>E-mail: dalpozzo@unical.it</affiliation><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</affiliation><affiliation>E-mail: dalpozzo@unical.it</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Giuseppe</namePart><namePart type="family">Bartoli</namePart><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Marcella</namePart><namePart type="family">Bosco</namePart><affiliation>Dipartimento di Chimica Organica ′A. Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Antonio</namePart><namePart type="family">De Nino</namePart><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Antonio</namePart><namePart type="family">Procopio</namePart><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Letizia</namePart><namePart type="family">Sambri</namePart><affiliation>Dipartimento di Chimica Organica ′A. Mangini′, Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Antonio</namePart><namePart type="family">Tagarelli</namePart><affiliation>Dipartimento di Chimica, Università della Calabria, Ponte Bucci, 87030 Arcavacata di Rende (Cs), Italy, Fax: (internat.) +39‐098/449‐2044</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="article" authority="ISTEX" authorityURI="https://content-type.data.istex.fr" valueURI="https://content-type.data.istex.fr/ark:/67375/XTP-6N5SZHKN-D">article</genre><originInfo><publisher>WILEY‐VCH Verlag GmbH</publisher><place><placeTerm type="text">Weinheim</placeTerm></place><dateIssued encoding="w3cdtf">2001-08</dateIssued><dateCaptured encoding="w3cdtf">2001-02-08</dateCaptured><copyrightDate encoding="w3cdtf">2001</copyrightDate></originInfo><language><languageTerm type="code" authority="rfc3066">en</languageTerm><languageTerm type="code" authority="iso639-2b">eng</languageTerm></language><physicalDescription><extent unit="figures">2</extent><extent unit="tables">3</extent><extent unit="references">26</extent></physicalDescription><abstract lang="en">α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to syn‐ and anti‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl4 in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the syn‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl3 in coordinating solvents such as THF, followed by reduction with LiBH4, predominantly led to the anti‐isomers, in agreement with an open‐chain transition state. The reduction to syn‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.</abstract><subject lang="en"><genre>keywords</genre><topic>Cyanides</topic><topic>Reductions</topic><topic>Asymmetric synthesis</topic><topic>Lewis acids</topic></subject><relatedItem type="host"><titleInfo><title>European Journal of Organic Chemistry</title></titleInfo><titleInfo type="abbreviated"><title>Eur. J. Org. 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